The thesis focuses on the research of molecular adsorption on surfaces and metallic electrodes. With that purpose, methods provided by quantum mechanics and devoted to the analysis of chemical systems were applied, specifically density functional theory. Theoretical outcome was compared with available experimental data, helping in interpreting them. The detailed analysis of a simple molecule as carbon monoxide was first accomplished, and subsequently extended to more complex molecules. Monocrystalline Pt(111) surfaces and also a bimetallic Pd/Pt(111) model were investigated, being the latter a system of growing interest in the field of electrochemistry. A tool allowing visualization of output files from VASP 4.5 code, named o2m, was also developed.
Comparison of experimental and theoretical IR spectra allows to state that CO molecules adsorb on top at monocrystalline Pt(111) electrodes, regardless of the electrode potential. However, the behaviour of the intenseless bands of spectra indicates a descent in coordination of CO molecule as potential increases. Results obtained with bimetallic Pd/Pt(111) electrode models reinforce the statement that CO stretching frequency is a very local property, only conditioned by the atoms directly involved in the chemisorption bond. The shift to higher frequencies as CO coverage increases is interpreted as a change of adsorption site, and not an external potential effect as in the platinum electrode case.
An exhaustive investigation of CO chemisorption on Pt(111), where periodic and cluster models were compared, points to fcc hollow position as the more stable adsorption site. This results are in clear contradiction with several experimental investigations showing that CO adsorbs on top sites. An approximation performed with the obtained results show that B3LYP functional and well converged models could restore the correct top adsorption site, since a more realistic description of the electronic states are achieved if compared with PW91 functional. HOMO-LUMO gap increases with the amount of exact exchange included in the hybrid functional, reducing the adsorbate LUMO metal d states interaction, previously overestimated at the most coordinated positions. The use of a GGA+U methodology also allows to shift the CO LUMO to higher energies.
A system consisting of a CO2 solution in contact with Pt(111) and Pd/Pt(111) electrodes was subsequently investigated. In the case of platinum electrode, the coexistence of both carbonate and bicarbonate anions adsorbed over short-bridge positions is suggested, with a relative surface coverage dependent on electrode applied potential and pH. However, for the Pd/Pt(111) electrode, only bicarbonate species is detected, irrespective of the external applied potential. Isotopic effects observed for one of the features in the spectra reinforce the assignment of the bands to normal modes of vibration for adsorbed bicarbonate species on the electrodic surface.
Eventually, structural parameters and theoretical IR spectrum for sulphate, propene and propylsulphate molecules adsorbed on Pt(111) were computed. The latter species was formed by the activation of propene moiety, due to the interactions with the sulphate molecule. The theoretical IR spectrum shows two characteristic features, which could be used as fingerprints to identify the alkylsulphate complex in an experimental setup. An oxidehidrogenation process carried out on such complex, led to the formation of an oximetalocycle, which structural parameters were calculated. From these results, it is suggested that such species could be an stable intermediate in the oxidation pathway for propene on Pt(111) surfaces.